The present invention relates to the hydroisomerization and dewaxing of hydrocarbon streams. In particular, the present invention relates to a catalyst combination that provides a high distillate yield with improved fluidity, viz., a reduced pour point and cloud point.
Most lubricating oil feedstocks must be dewaxed in order to manufacture finished products which will remain fluid down to the lowest temperature of use. Dewaxing is the process of separating or converting hydrocarbons which solidify readily (e.g., waxes) in petroleum fractions. Processes for dewaxing petroleum distillates have been known for a long time. As used herein, dewaxing means a reduction in at least some of the normal paraffin content of the feed. The reduction may be accomplished by isomerization of n-paraffins and/or cracking, or hydrocracking.
Dewaxing is required when highly paraffinic oils are to be used in products which need to flow at low temperatures, i.e., lubricating oils, heating oil, diesel fuel, and jet fuel. These oils contain high molecular weight straight chain and slightly branched paraffins which cause the oils to have high pour points and cloud points and, for jet fuels, high freeze points. In order to obtain adequately low pour points, these waxes must be wholly or partly removed or converted. In the past, various solvent removal techniques were used, such as MEK (methyl ethyl ketone-toluene solvent) dewaxing, which utilizes solvent dilution, followed by chilling to crystallize the wax, and filtration.
The decrease in demand for petroleum waxes as such, together with the increased demand for gasoline and distillate fuels, has made it desirable to find processes which not only remove the waxy components but which also convert these components into other materials of higher value. Catalytic dewaxing processes achieve this end by either of two methods or a combination thereof. The first method requires the selective cracking of the longer chain n-paraffins, to produce lower molecular weight products which may be removed by distillation. Processes of this kind are described, for example, in The Oil and Gas Journal, Jan. 6, 1975, pages 69 to 73 and U.S. Pat. No. 3,668,113. The second method requires the isomerization of straight chain paraffins and substantially straight chain paraffins to more branched species. Processes of this kind are described in U.S. Pat. No. 4,419,220 and U.S. Pat. No. 4,501,926.
To date, there have been a number of methods developed for dewaxing hydrocarbon feeds. Many dewaxing processes that are presently being used reduce the pour and cloud point of a hydrocarbon stream to acceptable levels at the price of producing more than a desirable amount of naphtha and light gas. An ideal economic fuel dewaxing process would reduce the pour point of the feed to acceptable levels while maximizing the yields of diesel fuel and heating oil and minimizing the yields of naphtha and light gas. Previous dewaxing processes have utilized zeolite hydrodewaxing catalysts including ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, mordenite, SAPO-11, and zeolite beta.
In order to obtain the desired selectivity, many previously known processes have used a zeolite catalyst having a pore size which admits the straight chain n-paraffins, either alone or with only slightly branched chain paraffins, but which excludes more highly branched materials, cycloaliphatics and aromatics. Zeolites such as ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38 have been proposed for this purpose in dewaxing processes and their use is described in U.S. Pat. Nos. 3,894,938; 4,176,050; 4,181,598; 4,222,855; 4,229,282; and 4,247,388. A dewaxing process employing synthetic offretite is described in U.S. Pat. No. 4,259,174. A hydrocracking process employing zeolite beta as the acidic component is described in U.S. Pat. No. 3,923,641.
Isomerization Dewaxing (xe2x80x9cIDWxe2x80x9d) technology is currently employed to lower the pour and cloud points of distillate fuel oils and gas oils to acceptable levels while minimizing the amount of naphtha and light gas. This goal is obtained through a series of mechanisms. The ideal end result is that the zeolite catalyst selectively isomerizes paraffins in the presence of aromatics. However, zeolite-based IDW also involves some conversion reactions, thereby resulting in significant yields of naphtha and C4-gases.
An improved dewaxing process is disclosed in U.S. Pat. No. 4,419,220 to La Pierre et al., the entire contents of which is incorporated herein by reference. This patent discloses that hydrocarbons such as distillate fuel oils and gas oils may be dewaxed primarily by isomerization of the waxy components over a zeolite beta catalyst. The process may be carried out in the presence or absence of added hydrogen, although operation with hydrogen is preferred. This process can be used for a variety of feedstocks including light gas oils, both raw and hydrotreated, vacuum gas oils and distillate fuel oils obtained by fluid catalytic cracking (FCC).
Although catalytic dewaxing (whether shape selective dewaxing or isomerization dewaxing) is an effective process, it has some limitations. A catalytic dewaxing process removes wax, but it does not change the end point of the product to a great extent. The problem is most severe when using a shape selective zeolite catalyst, such as ZSM-5, which selectively cracks the normal and slightly branched chain paraffins, but leaves most other components untouched. Thus, the feeds to most shape selective catalytic dewaxing processes are selected based on the desired product because the end point of the product usually sets the end point of the feed. This limits the available feedstocks, since these dewaxing processes can be used to dewax heavier feedstocks, but the heavier feedstocks cannot produce light products.
U.S. Pat. No. 4,446,007 to Smith, which is incorporated herein by reference, discloses a process for producing a relatively high octane gasoline by-product from the cracking of normal paraffins by increasing the hydrodewaxing temperature to at least 360xc2x0 C. within about seven days of start-up. This approach improves the economics of the dewaxing process by making the light by-products (the gasoline fraction) more valuable, but does not address the end-point problem. As a consequence, Smith does not take full advantage of the ability of the process to tolerate heavier feeds.
Other dewaxing processes reduce the pour point and cloud point of waxy feeds through the use of catalysts which isomerize paraffins in the presence of aromatics. These processes typically operate at relatively high temperatures and pressures, which results in extensive cracking and thereby degrades useful products to less valuable light gasses.
In light of the disadvantages of the conventional processes for improving distillate yield, there is a need for a new process that provides a high distillate yield with a reduced pour point and cloud point.
The present invention is a process for the isomerization dewaxing of a hydrocarbon feed. The process includes contacting the hydrocarbon feed with a catalyst containing a large pore crystalline molecular sieve having a Constraint Index of less than 2, an alpha value of less than 100 and an ultimate crystal size of less than 1 micron and a catalyst containing an intermediate pore crystalline molecular sieve having a Constraint Index greater than 2, an alpha value less than 100, an ultimate crystal size of less than 1 micron and an unidimensional or a non-intersecting two dimensional pore structure; under hydroprocessing conditions to produce a dewaxed product having improved fluidity. It is preferred that the process be carried out at superatmospheric hydrogen partial pressure.
The hydrocarbon feed preferably contains waxy components having a cloud point greater than about 0xc2x0 C., an ASTM D2887 end boiling point exceeding 275xc2x0 C., and a pour point greater than 5xc2x0 C. Preferably, the pour point of the feedstock is reduced by at least 5xc2x0 C.
The large pore crystalline molecular sieve is preferably selected from the group consisting of zeolite beta, mordenite, USY, ZSM-20, ZSM-4 (omega), zeolite L, VPI-5, SAPO-37, MeAlPO-37, AlPO-8, cloverite, CIT-1 and mixtures thereof. More preferably, the large pore crystalline molecular sieve is zeolite beta.
The intermediate pore crystalline molecular sieve is preferably selected from the group consisting of ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, MCM-22, SAPO-11, SAPO-5, MeAlPO-11, MeAlPO-5 and mixtures thereof More preferably, the intermediate pore crystalline molecular sieve is selected from the group consisting of ZSM-23, ZSM-48 and SAPO-11.
Preferably, the improved fluidity is manifested in a product having a reduced pour point and cloud point relative to the feed. Preferably, the pour point of the feedstock is reduced by at least 5xc2x0 C.
In one embodiment of the invention, the hydrocarbon feed is catalytically hydrotreated prior to contacting the catalyst system of the invention.
In another embodiment, the large pore crystalline molecular sieve and intermediate pore crystalline molecular sieve isomerization dewaxing catalysts are mixed together, combined to form a single combination catalyst by coextrusion or another forming method, stacked in a layered configuration, or contained in separate reactors.
Preferably, the process of the present invention is carried out with a ratio of large pore crystalline molecular sieve to intermediate pore crystalline molecular sieve from about 5:95 by weight to about 95:5 by weight.
The inventive process can be carried out in a reactor selected from the group consisting of a co-current flow gas-liquid reactor, a countercurent flow gas-liquid reactor, a sequential two stage reactor and a multiple reactor system.
The overall distillate yield of the inventive process preferably is greater than about 30% by weight.
The inventive process is preferably carried out under hydroprocessing conditions which include a temperature of from about 200xc2x0 C. to about 485xc2x0 C., of a hydrogen partial pressure of from about 1375 kPa to about 21,000 kPa, a hydrogen circulation rate of from about 100 to about 10,000 scf H2/BBL, and a liquid hourly space velocity (LHSV) of from about 0.1 to about 20 hrxe2x88x921 based on the total volume of catalyst.
The large pore crystalline molecular sieve and/or intermediate pore crystalline molecular sieve are preferably combined with a Group VIII metal selected from the group consisting of Pt, Pd, Ir, Rh, Ru, Co, Fe, Ni, and Os, or a combination of these metals. Preferred metals include Pt, Pd or a Pt-Pd combination.
In a particularly preferred embodiment, the hydrocarbon feed is contacted with the catalysts in an order starting with the large pore crystalline molecular sieve followed by the intermediate pore crystalline molecular sieve.
It is preferred that the large pore crystalline molecular sieve and/or the intermediate pore crystalline molecular sieve are combined with a binder material selected from the group consisting of clay, silica, alumina, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. In a preferred embodiment, the binder material is alumina.
Preferably, the large pore crystalline molecular sieve and/or the intermediate pore crystalline molecular sieve is/are combined with Pt, Pd or a Ptxe2x80x94Pd combination and an alumina binder.
The advantages of the present invention is that at the same product pour point, more distillate range products can be produced than expected by contacting a hydrocarbon feed with a combination of the large pore crystalline molecular sieve and the intermediate pore crystalline molecular sieve than by using these two molecular sieves separately. A further improvement in distillate yield than expected can be realized by contacting the feed sequentially, first with the large pore molecular sieve followed by the intermediate pore sieve.
Additional objects, advantages and novel features of the invention will be set forth in part in the description and examples which follow, and in part will become apparent to those skilled in the art upon examination of the following, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
In the present invention, heavy hydrocarbon streams are processed using a catalyst system containing a larger pore size isomerization catalyst, preferably containing zeolite beta or USY, and a smaller pore size isomerization catalyst, preferably containing ZSM-23, ZSM-48 or SAPO-11. The term xe2x80x9ccatalyst systemxe2x80x9d refers to isomerization dewaxing catalyst(s) containing a combination of the large pore crystalline molecular sieve and the intermediate pore crystalline molecular sieve. The combination can be in the form of separate catalysts, one containing the large pore sieve and one containing the intermediate pore sieve, that are mixed together; a single combination catalyst containing both the large pore and intermediate pore sieves; a stacked or layered configuration, where the different sieves are contacted sequentially; or a multiple reactor configuration, where the sieves are contained in separate reactors and contacted sequentially.
Preferably, the feedstream is processed in series, first by contacting with the larger pore size catalyst, followed by contacting with the smaller pore size catalyst. One configuration for processing the feedstream in series is to stack the two beds of catalyst with the bed containing the larger pore molecular sieve on top of the bed containing the intermediate pore molecular sieve. The more preferred configuration is to place the two different molecular sieve catalysts into two different reactors so that the operating temperatures can be controlled independently. The flow pattern would then be sequential with the oil flowing first over the larger pore molecular sieve catalyst and then over the intermediate pore catalyst. This maximizes distillate yields (distillate yield is that portion of the product that boils between 300xc2x0 F. and 750xc2x0 F. (145-400xc2x0 C.)) while producing a quality fuel with an acceptable pour point and cloud point. The isomerization dewaxing catalysts reduce the pour point of a fuel at lower conversion resulting in more of the desirable distillate products, while producing fewer unwanted light gases and naphtha. The sequential combination of catalysts used in the present invention, particularly zeolite beta followed by ZSM-23, ZSM-48 or SAPO-11, produces distillate yields that are significantly higher than the yields produced by using either of these zeolites alone or in a non-sequential mixture thereof.
As used in describing the present invention, the cloud point of an oil is the temperature at which paraffin wax or other solid substances begin to crystallize or separate from the solution, imparting a cloudy appearance to the oil when the oil is chilled under prescribed conditions. The conditions for measuring cloud point are described in ASTM D-2500. The pour point of an oil is the lowest temperature at which oil will pour or flow when it is chilled without disturbance under definite conditions. The conditions for measuring pour point are described in ASTM D-97.
The process of the present invention dewaxes hydrocarbon streams, such as hydrocracked bottoms, diesel fuels, and hydrotreated vacuum gas oils. This process operates by contacting the hydrocarbon feed stream with a large pore crystalline molecular sieve having a Constraint Index less than 2, an alpha valve less than 100 and an ultimate crystal size of less than 1 micron, and with an intermediate pore crystalline molecular sieve having a Constraint Index greater than 2, an alpha value of less than 100, an ultimate crystal size less than 1 micron and having a unidimensional or a non-intersecting two dimensional pore structure. In a preferred embodiment, the process operates by contacting the hydrocarbon streams with a noble metal/zeolite beta catalyst followed by a nobel metal/(ZSM-23, ZSM-48 or SAPO-11) catalyst to produce petroleum oils with acceptable pour and cloud points while maximizing the yield of distillate boiling range materials. The Pt/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11 catalysts are very effective at reducing the pour points of hydrocracked bottoms, diesel fuels and treated straight run gas oils at low conversion. When ZSM-23, ZSM-48 or SAPO-11 are used in sequence with zeolite beta, the distillate yields can be maximized while the light gas and naphtha yields are minimized.
The preferred Pt/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11 catalysts have significant dewaxing capabilities. At low 650xc2x0 F.+ conversions (between 10 and 20 wt %), the product pour point is from 30 to 50xc2x0 C. lower than the 100% Pt/zeolite beta catalyst and 50-80xc2x0 C. lower than the 100% Pt/USY catalyst. Another advantage of the ZSM-23, ZSM-48 and SAPO-11 catalysts are the low naphtha and light gas yields when compared to the Pt/zeolite beta catalyst. However, the activity of these intermediate pore molecular sieves would be lower than the conventional catalysts in terms of both conversion and dewaxing. Distillate yields (330-730xc2x0 F.) are also lower for these catalyst compared to the Pt/zeolite beta. The disclosure of ZSM-23 in U.S. Pat. Nos. 4,076,842; 4,490,342, 4,531,012; 4,619,820 and 5,405,596 is incorporated herein by reference. The disclosure of ZSM-48 in U.S. Pat. Nos. 4,397,827; 4,423,021; 4,448,675; 5,075,269; and 5,282,958; and the disclosure of SAPO-11 in U.S. Pat. No. 4,440,871 are also incorporated herein by reference.
It has been found that when used in series with the Pt/zeolite beta catalyst, the distillate yields of the Pt/ZSM-23, Pt/ZSM-48 and Pt/SAPO-11 catalysts are greatly improved. Preferably, the process of the present invention is carried out with a ratio of zeolite beta to the intermediate pore molecular sieve, i.e., ZSM-23, ZSM-48 or SAPO-11, from about 5:95 by wt to about 95:5 by wt. The overall distillate yield of the inventive process is at least 5% and preferably greater than about 30 wt %.
The large pore crystalline molecular sieve according to the invention has a Constraint Index of less than 2, an alpha value less than 100 and an ultimate crystal size of less than 1 micron, preferably less than about 0.5 microns. The method by which the Constraint Index is determined is fully described in U.S. Pat. No. 4,016,218, which is incorporated herein by reference.
The alpha value is an approximate indication of the catalytic cracking activity of the catalyst compared to a standard catalyst. The alpha test gives the relative rate constant (rate of normal hexane conversion per volume of catalyst per unit time) of the test catalyst relative to the standard catalyst which is taken as an alpha of 1 (Rate Constant =0.016 secxe2x88x921). The alpha test is describe in U.S. Pat. No. 3,354,078 and in J. Catalysis, 4, 527 (1965); 6, 278 (1966); and 61, 395 (1980), to which reference is made for a description of the test. The experimental conditions of the test used to determine the alpha values referred to in this specification include a constant temperature of 538xc2x0 C. and a variable flow rate as described in detail in J. Catalysis, 61, 395 (1980).
Small crystal (i.e., less than 1 micron) large pore molecular sieves according to the invention provide improved feedstock dewaxing via hydroisomerization over large crystal ( greater than 1 micron) large pore molecular sieves. U.S. Pat. No. 5,401,704 provides a good example of what is meant by crystal sizes less than 1 micron and serves as a good example of how small crystal large pore molecular sieves differ from standard, larger crystal molecular sieves, the entire contents of which is incorporated herein by reference.
Although the use of all large pore molecular sieves (i.e., those that have Constraint Indices less than two) according to the invention are contemplated, the large pore sieves are preferably selected from the group consisting of zeolite beta, mordentine, Y, ZSM-20, ZSM-4 (omega), zeolite L, VPI-5, SAPO-37, MeAlPO-37, AlPO-8 and cloverite.
Of these, zeolites beta and Y are the preferred large pore crystalline molecular sieves. Large pore zeolites such as beta and Y have a pore size sufficiently large enough to admit most of the components normally found in a feed stock, and generally have a pore size greater than seven Angstroms.
Preferably, the crystal size of the large pore molecular sieve is less than about 0.5 microns, more preferably less than about 0.2 microns. Of particular interest are smaller crystal versions of zeolites Y, beta, ZSM-20, mordenite, zeolite L, and zeolite Omega.
Methods for preparing zeolite Y are well known. Small crystal Y may be prepared by known methods including, for example, those methods describe in U.S. Pat. Nos. 3,864,282; 3,755,538 and 3,516,786; the entire contents of which are incorporated herein by reference. Zeolite beta is normally formed as a small crystal ( greater than 0.1 microns) when synthesized using basic conditions. Methods for synthesizing small crystal versions of the other aforementioned large pore zeolites have been published and are known in the art.
Of specific interest are zeolites Y and beta. Various forms of small crystal Y are useful in this invention. These include dealuminated Y where dealumination has been effected by steaming or acid extraction, ultrastable Y, also known as USY and various forms of cation exchanged Y and USY including, for example rare earth exchanged Y or ultrastable Y (i.e., REY or REUSY). The zeolite Y used in the hydroisomerization process may have a unit cell size (USC) of, for example, 24.6 Angstroms or less, e.g., 24.60 to 24.25 Angstroms. USY zeolites having a low unit cell size (USC) of, for example, 24.35 to 24.25, are particularly advantageous.
The ultrastable form of the Y-type zeolite, USY, can be prepared by successively base exchanging a Y-type zeolite with an aqueous solution of an ammonium salt, such as ammonium nitrate, until the alkali metal content of the Y-type zeolite is reduced to less than 4.0 wt %. The base exchanged zeolite is then calcined at a temperature of 540xc2x0 C. to 800xc2x0 C. for several hours, cooled and successively base exchanged with an aqueous solution of an ammonium salt until the alkali metal content is reduced to less than 1.0 wt %. This is followed by a final washing and calcination again at a temperature of 540xc2x0 C. to 800xc2x0 C. to produce an ultrastable zeolite Y. The sequence of ion exchange and heat treatment results in the substantial reduction of the alkali metal (e.g., Na) content of the original zeolite and results in a unit cell shrinkage which is believed to lead to the ultra high stability of the resulting Y-type zeolite.
The ultrastable zeolite Y may then be extracted with acid to produce a highly siliceous form of the zeolite.
The large pore zeolite catalyst used in this process will preferably also contain a hydrogenation metal, which may be a noble metal or metals, or a non-noble metal or metals. Suitable noble metals include the Group VIII noble metals, such as platinum and other members of the platinum group, such as iridium, palladium, and rhodium and combinations of these metals. Suitable non-noble metals include those of Groups VA, VIA, and VIIIA of the Periodic Table. Preferred non-noble metals are chromium, molybdenum, tungsten, cobalt, nickel, and combinations of these metals including cobalt-molybdenum, nickel-tungsten, nickel-molybdenum, and cobalt-nickel-tungsten. The non-noble metals may be pre-sulfided prior to use by exposure to a sulfur-containing gas such as hydrogen sulfide at an elevated temperature to convert the oxide form to the corresponding sulfide form of the metal.
The metal may be incorporated into the catalyst by any suitable method such as by impregnation or ion exchange into the zeolite. The metal may be incorporated in the form of a cationic, anionic, or neutral complex. Cationic complexes of the type Pt(NH3)4++ will be found convenient for exchanging metals into the zeolite. Anionic complexes such as the molybdate or metatungstate ions are also useful for impregnating metals onto the catalysts.
The amount of the hydrogenation metal is typically from 0.01 to 20 percent by weight, nominally 0.1 to 15 percent by weight based on the weight of the zeolite and the binder plus the weight of the hydrogenation metal. However, this will, of course, vary with the nature of the component, less of the highly active noble metals, particularly platinum or palladium, being required compared to the less active non-noble metals.
The intermediate pore crystalline molecular sieve according to the invention has a Constraint Index greater than 2, an alpha value less than 100, an ultimate crystal size of less than 1 micron, preferably less than about 0.5 microns, and has a unidimensional or a non-intersecting two dimensional pore structure. Examples of unidimensional intermediate pore molecular sieves include ZSM-22, ZSM-23, ZSM-48, SAPO-11, SAPO-5, MeAlPO-11 and MeAlPO-5 and an example of a non-intersecting two-dimensional intermediate pore molecular sieve is ZSM-35 (synthetic ferrierite).
The preferred intermediate pore crystalline molecular sieve is selected from the group consisting of ZSM-23, ZSM-48 and SAPO-11. ZSM-23, ZSM-48 and SAPO-11 are medium pore crystalline molecular sieves which can be identified in terms of moles of an oxide per 100 moles of silica and by specified x-ray powder diffraction patterns as described in U.S. Pat Nos. 4,076,842; 4,397,827; and 4,440,871; respectively, the entire contents of which are incorporated by reference.
The crystal size of the intermediate pore crystalline molecular sieve is also preferably less than about 0.5 microns, more preferably less than about 0.2 microns. The intermediate pore sieve is also preferably combined with a metal component as discussed with reference to the large pore sieves.
Both the large pore molecular sieve (e.g., zeolite beta) and intermediate pore crystalline molecular sieve (e.g., ZSM-23, ZSM-48 and SAPO-11) are preferably combined with a Group VIII metal selected from the group consisting of Pt, Pd, Ir, Rh, Ru, Co, Fe, Ni, and Os, and can use two or more metals in combination.
It is also desirable to incorporate the molecular sieve (i.e., the large pore and/or intermediate pore sieve) in a binder (or matrix) material. The binder materials include, but are not limited to, inorganic materials such as clay, silica and/or metal oxides. The metal oxide can be a metal oxide binder material such as alumina (Al2O3), silica-alumina, silica-magnesia, silica-zironcia, silica-thoria, silica-berylia, silica-titania, as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia. In one embodiment, the catalysts are ZSM-23, ZSM-48 or SAPO-11, and zeolite beta, which are both combined with alumina, and formed into a useable shape by methods such as extrusion or tabletting.
The present process may be used to dewax a variety of feedstocks ranging from relatively light distillate fractions up to high boiling stocks such as whole crude petroleum, cycle oils, gas oils, vacuum gas oils, furfural raffinates, deasphalted residues and other heavy oils. The feedstock will normally be a C10+ feedstock since lighter oils will usually be free of significant quantities of waxy components. However, the process is particularly useful with waxy distillate stocks to produce diesel fuels, gas oils, kerosenes, jet fuels, lubricating oil stocks, heating oils and other distillate fractions whose pour point and viscosity need to be maintained within certain specification limits. Lubricating oil stocks will generally boil above 230xc2x0 C. (450xc2x0 F.), more usually above 315xc2x0 C. (600xc2x0 F.).
Hydrocracked stocks can be used as a feedstock, as well as other distillate fractions which contain significant amounts of waxy n-paraffins produced by the removal of polycyclic aromatics. The feedstock for the present process will normally be a C10+ feedstock, preferably a C16+ feedstock, containing paraffins, olefins, naphthenes, aromatics, and heterocyclic compounds, with a substantial proportion of high molecular weight n-paraffins and slightly branched paraffins which contribute to the waxy nature of the feedstock.
The waxy feeds which are most benefited by the practice of the present invention will have relatively high pour points, usually above 80xc2x0 F. (26.7xc2x0 C.), but feeds with pour points ranging from 50xc2x0 F.(10xc2x0 C.) to 150xc2x0 F. (65.6xc2x0 C.) may also be used.
The feedstock is contacted with the isomerization dewaxing catalysts in the presence of hydrogen under hydroprocessing conditions of elevated temperature and pressure. Conditions of temperature, pressure, space velocity, hydrogen to feedstock ratio and hydrogen partial pressure which are similar to those used in conventional isomerization dewaxing operations can be employed herein.
Process temperatures of from about 200xc2x0 C. to about 485xc2x0 C. can be used although temperatures above about 420xc2x0 C. will normally not be employed as the reactions become unfavorable at temperatures above this point. Total pressure is in the range from about 344 to about 17,200 kPa with pressures above about 1375 kpa being preferred. The process is operated in the presence of hydrogen with hydrogen partial pressures of from about 300 kPa to about 21,000 kPa with pressures of from about 1375 to about 6900 being preferred. The hydrogen to feedstock ratio (hydrogen circulation rate) is normally of from about 100 to about 10,000 scf H2/BBL. The space velocity of the feedstock is normally of from about 0.1 to about 20 LHSV and, preferably, of from about 0.3 to about 4.0 LHSV.
Several types of reactors can be used to practice the present invention. The most common configuration is a downflow trickle bed (i.e., cocurrent gas-liquid. downflow reactor). Other reactors which can be used to practice the present invention include, but are not limited to, a cocurrent flow gas-liquid reactor, a countercurrent flow gas-liquid reactor, an ebullated bed reactor, a moving bed reactor, and a sequential two stage reactor wherein a gas or a liquid of the hydrocarbon feed cascades from a first stage to a second stage. The primary advantage of a countercurrent reactor is the removal of gas-phase heteroatom contaminants by countercurrent gas flow, thereby improving catalyst performance. In an ebullated bed reactor or a moving bed reactor, fresh catalyst can be continuously added and spent catalyst can be continuously withdrawn to improve process performance.
Within the same reactor, both small and large pore size dewaxing catalysts can be located in separate layers. In a preferred embodiment, zeolite beta is in the top layer; and one of ZSM-23, ZSM-48 or SAPO-11 is in the bottom layer. The ratio of intermediate pore to large pore size dewaxing catalysts can be varied to obtain the desired yield of distillates. The ratio of the catalysts will also vary based upon the feedstock and specific catalysts chosen. In general, the ratio of zeolite beta to intermediate pore sieve can vary over a wide range (i.e., from about 5:95 to about 95:5). The preferred ratio is dependent upon the refiner""s processing objective of tailoring dewaxing versus conversion.
In a preferred embodiment, the hydrocarbon feed is first passed over the catalyst in a first reactor containing the large pore size zeolite. The discharge from the first reactor is then passed over the smaller pore zeolite in a second reactor. More than two reactors in series can also be used. Ideally, the hydrocarbon feed passes over zeolite beta in the first reactor and subsequently passes over ZSM-23, ZSM-48 or SAPO-11 in a second reactor. The temperature of each reactor can be controlled and optimized for each catalyst. The temperature for the first reactor containing zeolite beta can suitably be of from about 200xc2x0 C. (392xc2x0 F.) to about 485xc2x0 C. (905xc2x0 F.), preferably of from about 250xc2x0 C. (482xc2x0 F.) to about 420xc2x0 C. (788xc2x0 F.). The temperature for the second reactor containing ZSM-23, ZSM-48 or SAPO-11 can be of from about 220xc2x0 C. (428xc2x0 F.) to about 485xc2x0 C. (905xc2x0 F.), preferably of from about 250xc2x0 C. (482xc2x0 F.) to about 400xc2x0 C. (752xc2x0 F.).
Various reactor configurations can be used for the inventive process. The feedstock can contact a fixed bed of catalyst, a fluidized bed or an ebullating bed. A simple configuration is a trickle-bed operation in which the liquid feed is allowed to trickle through a stationary fixed bed. Another reactor configuration employs a countercurrent process, i.e., the hydrocarbon feed flows down over a fixed catalyst bed while the H2 flows in the upward direction. The countercurrent configuration has the advantage that H2S and/or NH3 are removed overhead, and the noble metal catalyst is less impacted by these poisons.
A preliminary hydrotreating step to remove nitrogen and sulfur and to saturate aromatics to naphthenes without substantial boiling range conversion will usually improve catalyst performance and enable lower temperatures, higher space velocities, lower pressures or combinations of these conditions to be employed.
The present process proceeds mainly by isomerization of the n-paraffins to form branched chain products, with but a minor amount of cracking and the products will contain only a relatively small proportion of gas and light ends up to C5. Because of this, there is less need for removing the light ends which could have an adverse effect on the flash points of the product, as compared to processes using other catalysts. However, since some of these volatile materials will usually be present from cracking reactions, they can be removed by distillation.
The process of the present invention is selective for middle distillates. Middle distillates boil in the range of from about 165xc2x0 C. to about 345xc2x0 C. (about 330xc2x0 F. to about 650xc2x0 F.) and are used to provide distillate fuels including diesel and kerosene-type jet fuels and heating oils including No. 1 and No. 2 fuel oils. By isomerizing the waxy paraffins, premium middle distillate is produced. The product is highly iso-paraffinic with low pour point, suitable for jet fuel and diesel fuel.